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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2269—Heterocyclic carbenes
  • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
  • B01J31/2265—Carbenes or carbynes, i.e.(image)
  • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
  • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
  • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
  • C07F15/0046—Ruthenium compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
  • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
  • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
  • B01J2531/82—Metals of the platinum group
  • B01J2531/821—Ruthenium

Definitions

• the invention relates to the use of N-chelating ruthenium complexes of the general formula 1 as catalysts and / or (pre)catalysts in the olefin metathesis reaction.
• Grela presented the structure of the N-pyridine ligand complex [ Szadkowska, A., Gstrein, X., Burtscher, D., Jarzembska, K., Wo ⁇ niak, K., Slugovc, C., Grela, K., Organometallics 2010, 29,117-124 ] and a series of complexes having a secondary amine in the benzylidene ligand (3) [ ⁇ ukowska, K., Szadkowska, A., Pazio, A., Wo ⁇ niak, K., Grela, K., Organometallics 2012, 31, 462-469 ].
• Another example is a complex having a ligand with a chelating nitrogen atom which alkyl substituents together with the nitrogen atom form a pyrrolidine ring (4)
• the (pre)catalysts cited above are examples of latent N-chelating complexes requiring an elevated temperature or addition of an acid, e.g. Lewis acid for activation. Their latency is caused by the high electron density on the nitrogen atom, which is associated with the strong interaction of Ru-N and slow initiation.
• Catalysts of this type are used as initiators of the ROMP reaction ( EP 2452958 B1 ) .
• ROMP reaction EP 2452958 B1
• RU 2462308 C1 and WO 2015/126279 A1 7a-c complexes are described, as latent and useful in the DCPD metathesis polymerization reaction.
• the initiation rate of catalyst depends among others on the binding strength between Ru-N (or -Ru-another chelating heteroatom) in the benzylidene ligand. In the case of strong Ru-N interaction, the catalyst is initiating slowly (latent requires thermal or chemical activation) and is the most often used in ROMP reactions.
• a nitrogen atom in the benzylidene ligand strongly interacts with ruthenium. The electron density on the nitrogen atom is increased by alkyl substituents. The electron density can be correlated with the change of basicity in a series of differently substituted amines [ Hoefnagel, A. J., Hoefnalgel, M. A., Wepster, B. M., J. Org. Chem. 1981 46, 4209-4211 ].
• Complexes of formula 1 according to the invention are applicable in a wide range of reactions. Ring closing metathesis(RCM), cross metathesis (CM) and homometathesis (self-CM) can be performed with good results.
• (Pre)catalysts of the general Formula 1 in metathesis reactions show much higher activity than complexes having alkyl substituents on the nitrogen atom (Examples I-IV).
• the complexes of formula 1 used in a small amount catalyze reactions in a wide range of concentrations and temperatures, which greatly facilitates the development of an efficient process.
• the above-mentioned properties are desirable from the point of industrial application of ruthenium complexes as (pre)catalysts for the metathesis reaction.
• the compound is represented by formula 1 wherein:
• the ruthenium compound of formula 1 has the structural formula selected from the following formula 1a-1g;
• the reaction is carried out in an organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tetrabutyl methyl ether, cyclopentyl methyl ether or without a solvent.
• organic solvent such as toluene, benzene, mesitylene, dichloromethane, ethyl acetate, methyl acetate, tetrabutyl methyl ether, cyclopentyl methyl ether or without a solvent.
• the reaction is carried out at a temperature of from 0 to 150°C.
• the reaction is carried out at a temperature of from 20 to 120 °C.
• the reaction is carried out from 1 minute to 24 hours.
• compound 1 is used in an amount not greater than 0,5 mol%.
• compound 1 is added to the reaction mixture in solid form and/or in the form of a solution in an organic solvent.
• halogen atom represents an element selected from F, Cl, Br, I.
• carbene represents a particle containing an inert carbon atom with a valence number of two and two unpaired valence electrons.
• the term “carbene” also includes carbene analogues in which the carbon atom is replaced with another chemical element such as boron, silicon, germanium, tin, lead, nitrogen, phosphorus, sulfur, selenium, tellurium.
• alkyl refers to a saturated, linear, or branched hydrocarbon substituent with an indicated number of carbon atoms.
• alkyl substituent are -methyl, -ethyl, -n- propyl, - n -butyl, - n -pentyl, - n -hexyl, - n -heptyl, - n -octyl, - n -nonyl, and - n -decyl.
• Representative branched -(C1-C10)alkyles include -isopropyl, - sec -butyl, -isobutyl, -tert- butyl, -isopentyl, -neopentyl, -1-methylbutyl, -2-methylbutyl, -3-methylbutyl, -1 , 1-dimethylpropyl, -1,2-dimethylpropyl, -1-methylpentyl, -2-methylpentyl, -3-methylpentyl, -4-methylpentyl, -1-ethylbutyl, -2-ethylbutyl, -3-ethylbutyl, -1,1-dimethylbutyl, -1,2-dimethylbutyl, -1,3-dimethylbutyl, -2,2-dimethylbutyl, -2,3-dimethylbutyl, -3,3-dimethylbutyl,
• alkoxy refers to an alkyl substituent as defined above linked through an oxygen atom.
• perfluoroalkyl represents an alkyl group as defined above in which all hydrogen atoms have been replaced by the same or different halogen atoms.
• cycloalkyl refers to a saturated mono- or polycyclic hydrocarbon substituent with an indicated number of carbon atoms.
• examples of the cycloalkyl substituent are - cyclopropyl, -cyclobutyl, -cyclopentyl, -cyclohexyl, -cycloheptyl, cyclooktyl, -cyclononyl, - cyclodecyl, and the like.
• alkenyl refers to a saturated, linear, or branched non-cyclic hydrocarbon substituent having an indicated number of carbon atoms and containing at least one carbon-carbon double bond.
• alkenyl substituent are -vinyl, -allyl, -1-butenyl, -2-butenyl, -isobutylenyl, -1-pentenyl, -2-pentenyl, -3-methyl-1-butenyl, -2-methyl-2-butenyl, - 2,3-di-methyl-2-butenyl, -1-hexenyl, -2-hexenyl, -3-hexenyl, -1-heptenyl, -2-heptenyl, -3-heptenyl, -1-octenyl, -2-octenyl, -3-octenyl, -1-nonenyl, -2-nonenyl, -3-n
• aryl refers to an aromatic mono- or polycyclic hydrocarbon substituent with an indicated number of carbon atoms.
• Examples of an aryl substituent are -phenyl, -tolyl, -silyl, - naphthyl, -2,4,6-trimethylphenyl, -2-fluorophenyl, -4-fluorophenyl, -2,4,6-trifluorophenyl, - 2,6-difluorophenyl, -4-nitrophenyl and the like.
• aralkyl refers to an alkyl substituent as defined above substituted with at least one aryl as defined above.
• Examples of aralkyl substituent are -benzyl, -diphenylmethyl, - triphenylmethyl and the like.
• heteroaryl refers to an aromatic mono- or polycyclic hydrocarbon substituent with an indicated number of carbon atoms in which at least one carbon atom has been replaced by a heteroatom selected from O, N and S.
• a heteroaryl substituent are - furyl, -thienyl, -imidazolyl, -oxazolyl, -thiazolyl, -isoxazolyl, -triazolyl, -oxadiazolyl, - thiadiazolyl, -tetrazolyl, -pyridyl, -pyrimidyl, -triazinyl, -indolyl, -benzo[b]furyl, - benzo[b]thienyl, -indazolyl, -benzoimidazolyl, -azazolyl, -quinolyl, -isoquinolyl, -carbazolyl, and the like.
• heterocycle refers to a saturated or partially unsaturated, mono- or polycyclic hydrocarbon substituent with an indicated number of carbon atoms in which at least one carbon atom has been replaced with a heteroatom selected from O, N and S.
• a heterocycle substituent are furyl, thiophenyl, pyrrolyl, oxazolyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, triazinyl, pyrrolidinonyl, pyrrolidinyl, hydantoinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydrothiophenyl, quinolinyl, isoquinolinyl, chromonyl, coumarinyl, indolyl, indolizinyl, benzo[b]furanyl, benzo[b]thiophenyl, ind
• neutral ligand refers to a non-charged substituent capable of coordinating with a metallic center (a ruthenium atom).
• ligands can be: amines, phosphines and their oxides, alkyl and aryl phosphites and phosphates, arsines and their oxides, ethers, alkyl and aryl sulphides, coordinated hydrocarbons, alkyl halides and aryl halides.
• anionic ligand refers to a substituent capable of coordinating with a metallic center (a ruthenium atom) having a charge capable of partially or completely compensating the charge of the metallic center.
• ligands may be fluoride anions, chloride, bromide, iodide, cyanide, cyanate and thiocyanate anions, carboxylic acid anions, alcohol anions, phenol anions, thiols and thiophene anions, hydrocarbon anions with delocalized charge (e.g. cyclopentadiene), anions of (organo)sulfuric and (organo)phosphoric acids and their esters (such as e.g.
• the anion ligand may have L 1 , L 2 and L 3 groups, linked in the same way as the catechol anion, the acetylacetone anion, the salicylic aldehyde anion.
• Anion ligands (X 1 , X 2 ) as well as neutral ligands (L 1 , L 2 , L 3 ) can be linked to each other to form multidentate ligands, e.g. a bidentate ligand (X 1 -X 2 ), a tridential ligand (X 1 -X 2 -L 1 ), a tetradentate ligand (X 1 -X 2 -L 1 -L 2 ), a bidentate ligand (X 1 -L 1 ), a tridential ligand (X 1 -L 1 -L 2 ), a tetradentate ligand (X 1 -L 1 -L 2 -L 3 ), a bidentate ligand (L 1 -L 2 ), a tridential ligand (L 1 -L 2 -L 3 ).
• ligands are: catechol anion, acetylacetone anion and salicylic
• heteroatom represents an atom selected from the group of oxygen, sulfur, nitrogen, phosphorus and others.
• Diethyl malonate (S1), ethyl undecenoate (S3), acrylonitrile and methyl stearate are commercially available compounds.
• Diethyl (2,2-dimethylallyl)malonate (S2) was prepared according to the procedure from literature, S1 and S3 were distilled under reduced pressure and stored over activated alumina. Acrylonitrile was dried with 4 ⁇ molecular sieves and deoxygenated with argon. All reactions were carried out under argon. Toluene was washed with citric acid, water, dried with 4 ⁇ molecular sieves and deoxidized with argon.
• composition of the reaction mixtures was examined by gas chromatography using a PerkinElmer Clarus 680 GC apparatus equipped with a GL Sciences InertCap ® 5MS/NP capillary column.
• reaction mixtures were identified by comparing the retention times with commercial standards or isolated from reaction mixtures for which the structure was confirmed by NMR.
• the C1-C2 (pre)catalysts known in the state of the art initiate the metathesis reaction of S3 without the addition of an activator, while their activity is significantly lower than (pre)catalysts 1a-d.
• the precipitated product was filtered and washed with ethyl acetate.
• the ammonium salt was obtained as a white crystalline solid (3.880 g, 98%).
• the ammonium salt obtained in the previous step was dissolved in ethanol (96%, 50 ml) and NaOH (0.590 g, 14.8 mmol, 1.5 molar equivalent) was added. It was heated in reflux with stirring for 2 hours. The mixture was cooled and methanol was evaporated, yielding a yellow oil. It was dissolved in methylene chloride, washed with water. It was dried over Na 2 SO 4 , filtered and concentrated to dryness to give a slightly yellow oil (2.605 g, 84%).

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